EP1017747B1 - Materials which can be thermally coated with a polymerizable component - Google Patents

Materials which can be thermally coated with a polymerizable component Download PDF

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Publication number
EP1017747B1
EP1017747B1 EP98951411A EP98951411A EP1017747B1 EP 1017747 B1 EP1017747 B1 EP 1017747B1 EP 98951411 A EP98951411 A EP 98951411A EP 98951411 A EP98951411 A EP 98951411A EP 1017747 B1 EP1017747 B1 EP 1017747B1
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Prior art keywords
reactive
meth
polymers
plastisols
plastisols according
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EP98951411A
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German (de)
French (fr)
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EP1017747A1 (en
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Volker Kerscher
Thomas Süfke
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material

Definitions

  • the invention relates to so-called reactive plastisols, i.e. thermal Filmable polymers, which are preferably based on (meth) acrylates and / or styrene are built up, a low molecular weight or oligomeric Contain plasticizers and a reactive monomer component.
  • reactive plastisols i.e. thermal Filmable polymers, which are preferably based on (meth) acrylates and / or styrene are built up, a low molecular weight or oligomeric Contain plasticizers and a reactive monomer component.
  • Plastisols are suspensions or dispersions of finer particles Polymer particles in certain liquid organic media, so-called plasticizers. Those in the plasticizer phase Finely dispersed polymer particles form at room temperature Room temperature a paste. But they melt into one for them Plastisol processing typical "gelling process" at temperatures of in usually> 100 ° C, usually> 150 ° C and form below Absorption of the plasticizer by the polymers is a uniform plastic matrix.
  • Plastisols based on PVC have due to their favorable application technology Properties (mechanical stability, adhesion on Substrates, etc.) widespread use, especially on the Coating sector found. (See Kunststoff-Handbuch, 2nd ed. Ed. H.K. Felger Vol. 2/2 pp. 1077 - 1124; 854 - 869, Hanser-Verlag 1985).
  • plastisols have also been used with beneficial properties developed on a poly (meth) acrylate basis as so-called PAMA plastisols (DE-A 24 54 235, US-A 4 071 653; DE-A 40 30 080, US-A 5 120 795).
  • plasticizers are esters of phthalic acid, citric acid esters, however also known as oligomeric compounds.
  • the stability of the plasticizers is characteristic of plastisols and polymer formed pastes at storage temperature.
  • the norm lies here i.a. at> 30 days.
  • the thermal filming is usually after application to the substrate to be coated Heats to> 150 ° C within a few minutes.
  • the effect lies in the crosslinking nature of the added compounds justified.
  • the polymerization of such additives occurs at the same time physical gelation when heated by thermal polymerization a.
  • the disintegration characteristics of the added initiators becomes adjusted to the setting temperature used.
  • DE-PS 25 43 542 (Röhm GmbH) describes a method for production of a plastisol by emulsion polymerization of a monomer Mixture of methacrylic acid methyl esters, monomers with a basic nitrogen atom and others copolymerizable therewith Monomers. It differs from the plastisols according to the invention the composition by the presence of monomers with a basic nitrogen atom.
  • the disadvantages of the plastisols of the prior art are in particular their lack of hardness and abrasion resistance, which is directly related to the high plasticizer content, guide value approx. 60% by weight, been registered. This disadvantage is especially true for Polyalkyl (meth) acrylate plastisols. An increase in the solids content with the aim of achieving improved mechanical properties however, this is countered by the greatly increased viscosity of plastisols rich in solids.
  • the object was therefore to improve plastisols with Performance properties, especially improved mechanical ones Properties and sufficient storage stability To provide polyalkyl (meth) acrylate base.
  • thermally filmable Polymers P are known per se as base polymers for plastisols.
  • the present invention is of particular importance with regard to the so-called PAMA plastisols formed from poly (meth) acrylic acid esters P-M.
  • the polymer content is preferably in disperse form, in particular as a spray-dried emulsion polymer.
  • the main monomer component of the thermally filmable polymer P is preferably methyl methacrylate or styrene, which as a rule make up over 60% by weight, in particular> 70 and preferably 80-99% by weight, based on PM.
  • Polar comonomers are to be understood as meaning, in particular, those which contain the heteroatoms nitrogen and / or oxygen or - less preferably sulfur - especially if they have hydrogen bonded to them at the same time.
  • the monomers of the formula III are preferably C4-alkyl esters acrylic acid or methacrylic acid, e.g. Isobutyl (meth) acrylate or n-butyl (meth) acrylate or around Ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate.
  • Poly (meth) acrylic acid esters P-M with a core-shell structure are of particular interest.
  • the thermally filmable polymers especially those based on PMMA be 60 to 10 percent by weight, based on the total mass of Components (A) - (E), specifically about 40% by weight, are given.
  • the molecular weight Mw is the Poly (meth) acrylic acid ester P-M in the range 20,000 to 200,000, especially 30,000 to 150,000 daltons.
  • the proportion of reactive monomers (B) is set according to the Formulations expediently radical initiators, such as those already for the preparation of the poly (meth) acrylic acid esters P-M described in Quantities of about 0.5% by weight, based on the reactive monomers (B) to.
  • the reactive plastisols according to the invention also contain, as further crosslinking monomer component (D), known crosslinkers in amounts of up to 20% by weight, preferably 0.1 to 10% by weight, based on the thermally filmable polymers P.
  • crosslinking monomers contain several radically polymerizable units in the same molecule, such as, for example, (meth) acrylic acid esters of polyhydric alcohols. Examples include trimethylolpropane tri (meth) acrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate.
  • Components (A) and (B) are generally in a weight ratio of 20 to 1 to 1 to 20.
  • the usual emulsifiers also come with an HLB value over 12, especially anionic emulsifiers, such as the salts long-chain paraffin sulfonic acid is an option.
  • the procedure is such that one to an aqueous template with initiator / emulsifier at elevated temperature, for example about 80 ° C, an aqueous emulsion of the monomers with Initiator with stirring within a certain time, for example 11 ⁇ 2 ( ⁇ 1 ⁇ 2) hour added dropwise and to complete the polymerization holds for about the same period at an elevated temperature.
  • an aqueous emulsion of the monomers with Initiator with stirring within a certain time, for example 11 ⁇ 2 ( ⁇ 1 ⁇ 2) hour added dropwise and to complete the polymerization holds for about the same period at an elevated temperature.
  • the reaction mixture can be spray-dried.
  • Inorganic peroxides such as potassium or Ammonium peroxydisulfate in amounts of 0.001 to 0.2% by weight, based on proven on the monomers.
  • redox systems consisting of a Peroxide component and a reducing component such as a reducing salt of an oxo-sulfuric acid can be use.
  • the molecular weight can by Addition of regulators, usually sulfur regulators, especially Alkyl mercaptans such as dodecyl mercaptan, lauryl mercaptan in Amounts of usually about 0.05 to 0.5 wt .-%, based on the Monomers are regulated.
  • the molecular weight is generally in Range 20,000-200,000 daltons.
  • Spray drying can also be carried out in a known manner.
  • So-called spray towers are used on a large scale usually in cocurrent with the dispersion sprayed in from above be flowed through with hot air downwards.
  • the dispersion is through one or many nozzles sprayed or preferably by means of one quickly rotating perforated disc atomized.
  • the incoming hot air has a Temperature from 100 ° C to 250 ° C, preferably from 150 ° C to 250 ° C.
  • the outlet temperature of the air is decisive, i.e. the temperature at which the dried powder granules at the base of the spray tower or in separated from the air flow by a cyclone separator. These The temperature should be below the temperature at which the Emulsion polymer would sinter or melt. In many cases it is an outlet temperature of 50 ° C - 90 ° C is well suited.
  • the outlet temperature can be varied with a constant air flow regulate the amount of dispersion continuously sprayed in per unit of time.
  • the PM polymers obtained by spray drying the polymer dispersion have a primary particle size in the range from 0.1 to 5 ⁇ m. (Determination according to Ullmann's Encyclopedia of Technological Chemistry, 4th Edition, Vol. 5 , pp. 725-752).
  • the particle size distribution can be determined by measuring the light absorbance of a suspension of the particles in water flowing through the measuring cell of a measuring device ("Kratel Partoskop F" from Kratel GmbH, Göttigen).
  • a secondary aggregation of the primary particles can lead to agglomerates in the size range 5-100 ⁇ m, but these can also be used for the purposes of the present invention.
  • Plasticizers W of category (C) are known per se Plasticizers in question, such as B. the alkyl esters of phthalic acid, the Adipic acid, sebacic acid, chlorinated paraffins, trialkyl phosphates, aliphatic or araliphatic polyester in addition to plasticizers with medium polarity such as higher polyglycols, phthalic acid polyester or Adipic acid polyester; a.
  • a hint can be that in the As a rule, all plasticizers suitable for PVC can also be used can, taking the group of phthalate plasticizers because of their outstanding technical importance is particularly to be emphasized.
  • a detailed description of suitable plasticizers can be found in Kunststoff-Handbuch ed. H.K. Felger Vol.
  • DE-C 25 43 542 can also select suitable plasticizers can be removed.
  • plasticizers W are generally used in proportions of 5 to 200 parts by weight per 100 parts by weight of the thermally filmable polymers P.
  • the ratio between plasticizer W and the monomers of component (B) can be adjusted practically as desired.
  • the usual formulation contains, for example, 10 parts by weight of monomer (B) [including 0.5% by weight of initiator based on content (B)] approx. 40 Parts by weight of thermally filmable polymers P, 50 parts by weight Plasticizer W.
  • the resulting plastisols according to the invention have very good performance properties. Their tensile strength and the blocking resistance of the products should be emphasized, for example. Pot lives of more than 30 days are guaranteed. Comparative products with a content of 40% by weight of polymer and 60% by weight of plasticizer have a very low tensile strength and a sticky surface. The ratio between plasticizer and component (C) can be adjusted as desired.
  • the reactive plastisols still contain auxiliaries known per se, such as adhesion promoters, wetting agents, leveling agents, propellants in proportions of up to 5% by weight (based on the reactive plastisols).
  • auxiliaries known per se, such as adhesion promoters, wetting agents, leveling agents, propellants in proportions of up to 5% by weight (based on the reactive plastisols).
  • the components for the reactive plastisols according to the invention can be mixed using various types of mixers.
  • slow-running planetary agitators, high-speed mixers or dissolvers, horizontal turbo mixers and three-roll mills are preferred; the choice being influenced by the viscosity of the plastisols produced. (. See HF Mark et al, Encyclopedia of Polymer Science and Engineering 2nd Ed Vol 17, 365 -... 866 J. Wiley 1989). Mixing is carried out until the mass has become homogeneous.
  • the mass can be layered in thicknesses of 1 - 5 mm preferably at temperatures of 100-200 ° C, im generally be gelled within 30 to 2 minutes. You get in usually a transparent flexible film.
  • the reactive plastisols obtainable according to the present invention are suitable for many applications, for example by the Areas of application for PVC and PAMA plastisols are: Textile coating agents, floor coverings e.g. flexible floor coverings, Underbody protection, spot welding pastes or coating agents for flexible substances.
  • the monomers according to (B) have a very high boiling point and have practically no smell worth mentioning.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Graft Or Block Polymers (AREA)
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Abstract

The invention relates to reactive polysols with a reactive monomer portion which is polymerized during thermal coating. The polysols exhibit good mechanical properties. A monofunctional (meth)acrylate monomer of formula (1) is used as reactive monomer component.

Description

Die Erfindung betrifft sogenannte Reaktivplastisole, d.h. thermisch verfilmbare Polymere die bevorzugt auf Basis von (Meth)acrylaten und/oder Styrol aufgebaut sind, einen niedermolekularen oder oligomeren Weichmacher und einen reaktiven Monomeranteil enthalten.The invention relates to so-called reactive plastisols, i.e. thermal Filmable polymers, which are preferably based on (meth) acrylates and / or styrene are built up, a low molecular weight or oligomeric Contain plasticizers and a reactive monomer component.

Stand der TechnikState of the art

Plastisole sind Suspensionen oder Dispersionen feinteiliger Polymerpartikel in bestimmten flüssigen organischen Medien, sogenannten Weichmachern. Die in der Weichmacherphase bei Raumtemperatur feindispers verteilten Polymerpartikel bilden bei Raumtemperatur eine Paste. Sie schmelzen aber in einem für die Plastisolverarbeitung typischen "Gelierprozeß" bei Temperaturen von in der Regel > 100 °C, üblicherweise > 150 °C auf und bilden unter Absorption des Weichmachers durch die Polymeren eine einheitliche plastische Matrix.Plastisols are suspensions or dispersions of finer particles Polymer particles in certain liquid organic media, so-called plasticizers. Those in the plasticizer phase Finely dispersed polymer particles form at room temperature Room temperature a paste. But they melt into one for them Plastisol processing typical "gelling process" at temperatures of in usually> 100 ° C, usually> 150 ° C and form below Absorption of the plasticizer by the polymers is a uniform plastic matrix.

Typische Vertreter von thermoplastischen feinteiligen Kunststoffen für die Herstellung von Plastisolen sind:

  • Polyvinylchlorid (PVC)
  • Polymethylmethacrylat (PMMA)
  • Polyalkylmethacrylat (PAMA), z.B.
    Polymethylmethacrylatcopolymere
  • Polyvinylchlorid-Copolymere (PVC/PVAc)
Typical representatives of thermoplastic finely divided plastics for the production of plastisols are:
  • Polyvinyl chloride (PVC)
  • Polymethyl methacrylate (PMMA)
  • Polyalkyl methacrylate (PAMA), e.g.
    Polymethyl methacrylate copolymers
  • Polyvinyl chloride copolymers (PVC / PVAc)

Plastisole auf PVC-Basis haben aufgrund ihrer günstigen anwendungstechnischen Eigenschaften (mechanische Stabilität, Haftung auf Untergründen usw.) weite Verbreitung, insbesondere auf dem Beschichtungssektor gefunden. (Vgl. Kunststoff-Handbuch, 2. Aufl. Ed. H.K. Felger Bd. 2/2 S. 1077 - 1124; 854 - 869, Hanser-Verlag 1985).Plastisols based on PVC have due to their favorable application technology Properties (mechanical stability, adhesion on Substrates, etc.) widespread use, especially on the Coating sector found. (See Kunststoff-Handbuch, 2nd ed. Ed. H.K. Felger Vol. 2/2 pp. 1077 - 1124; 854 - 869, Hanser-Verlag 1985).

In jüngerer Zeit wurden Plastisole mit vorteilhaften Eigenschaften auch auf Poly(meth)acrylat-Basis als sogenannte PAMA-Plastisole entwickelt (DE-A 24 54 235, US-A 4 071 653; DE-A 40 30 080, US-A 5 120 795).More recently, plastisols have also been used with beneficial properties developed on a poly (meth) acrylate basis as so-called PAMA plastisols (DE-A 24 54 235, US-A 4 071 653; DE-A 40 30 080, US-A 5 120 795).

Als Weichmacher sind Ester der Phthalsäure, Citronensäureester, aber auch oligomere Verbindungen bekannt.As plasticizers are esters of phthalic acid, citric acid esters, however also known as oligomeric compounds.

Kennzeichnend für Plastisole ist die Stabilität der auch Weichmacher und Polymer gebildeten Pasten bei Lagertemperatur. Die Norm liegt hier i.a. bei > 30 Tagen. Die thermische Verfilmung wird in der Regel nach dem Aufbringen auf den zu beschichtenden Untergrund durch Erhitzen auf > 150 °C innerhalb weniger Minuten bewirkt. The stability of the plasticizers is characteristic of plastisols and polymer formed pastes at storage temperature. The norm lies here i.a. at> 30 days. The thermal filming is usually after application to the substrate to be coated Heats to> 150 ° C within a few minutes.

Es ist weiterhin bekannt, den Plastisolen zur Haftvermittlung auf metallische Untergründen sowie zur Modifikation der Festigkeit und Härte polymerisierbare vernetzende Verbindung wie (Meth)acrylsäureester mehrwertiger Alkohole wie z.B. Trimethylolpropantrimethacrylat zuzusetzen. Die Einsatzmöglichkeiten derartiger Zusätze sind jedoch mengenmäßig begrenzt, da es bei größeren Zusatzmengen, z.B. oberhalb 5 Gew.%, zu einer starken Versprödung der gelierten Beschichtungsmasse kommt.It is also known to use plastisols to promote adhesion metallic substrates as well as to modify the strength and Hardness polymerizable crosslinking compound such as (Meth) acrylic acid esters of polyhydric alcohols such as e.g. Add trimethylolpropane trimethacrylate. The possible uses Such additives are, however, limited in terms of quantity, as there are larger added amounts, e.g. above 5% by weight, to a strong The gelled coating mass becomes brittle.

Der Effekt liegt in der vernetzenden Natur der zugesetzten Verbindungen begründet. Die Polymerisation solcher Zusätze tritt zeitgleich zur physikalischen Gelierung beim Erhitzen durch thermische Polymerisation ein. Die Zerfallscharakteristik der zugesetzten Initiatoren wird dabei der angewendeten Geliertemperatur angepaßt.The effect lies in the crosslinking nature of the added compounds justified. The polymerization of such additives occurs at the same time physical gelation when heated by thermal polymerization a. The disintegration characteristics of the added initiators becomes adjusted to the setting temperature used.

DE-PS 25 43 542 (Röhm GmbH) beschreibt ein Verfahren zur Herstellung eines Plastisols durch Emulsionspolymerisation eines monomeren Gemisches aus Methacrylsäuremethylestem, Monomeren mit einem basischem Stickstoffatom und andere damit mischpolymeriserbare Monomeren. Von den erfindungsgemäßen Plastisolen unterscheidet sich die Zusammensetzung durch die Anwesenheit von Monomeren mit einem basischem Stickstoffatom.DE-PS 25 43 542 (Röhm GmbH) describes a method for production of a plastisol by emulsion polymerization of a monomer Mixture of methacrylic acid methyl esters, monomers with a basic nitrogen atom and others copolymerizable therewith Monomers. It differs from the plastisols according to the invention the composition by the presence of monomers with a basic nitrogen atom.

US-PS 5,298,542 (Nippon Ceon Coop.) beschreibt Acrylesterplastisol-Zusammensetzungen. Auch hier wird das spezielle Monomer der Erfindung wie es in Komponente (B) beschrieben wird, nicht erwähnt. U.S. Patent 5,298,542 (Nippon Ceon Coop.) Describes acrylic ester plastisol compositions. Here, too, the special monomer is the Invention as described in component (B) is not mentioned.

US-PS 5,324,762 (ICI) beschreibt ein Plastisol aus Gemischen aus Methylmethacrylat und Isobutylmethacrylatcopolymeren. Weitere Monomerkomponenten wie beispielsweise Isobornylmethacrylat und ihre spezifischen Vorteile werden nicht offenbart.US Pat. No. 5,324,762 (ICI) describes a plastisol made from mixtures Methyl methacrylate and isobutyl methacrylate copolymers. Further Monomer components such as isobornyl methacrylate and theirs specific advantages are not disclosed.

Aufgabe und LösungTask and solution

Als Nachteil der Plastisole des Standes der Technik sind insbesondere deren mangelnde Härte und Abriebfestigkeit, die unmittelbar mit dem hohen Weichmachergehalt, Richtwert ca. 60 Gew.-%, zusammenhängen, registriert worden. Dieser Nachteil gilt insbesondere auch für Polyalkyl(meth)acrylat-Plastisole. Einer Anhebung des Feststoffgehalts mit dem Ziel, verbesserte mechanische Eigenschaften zu erreichen, steht jedoch die stark erhöhte Viskosität festkörperreicher Plastisole entgegen.The disadvantages of the plastisols of the prior art are in particular their lack of hardness and abrasion resistance, which is directly related to the high plasticizer content, guide value approx. 60% by weight, been registered. This disadvantage is especially true for Polyalkyl (meth) acrylate plastisols. An increase in the solids content with the aim of achieving improved mechanical properties however, this is countered by the greatly increased viscosity of plastisols rich in solids.

Es bestand daher die Aufgabe, Plastisole mit verbesserten Gebrauchseigenschaften, insbesondere verbesserten mechanischen Eigenschaften und ausreichender Lagerstabilität auf Polyalkyl(meth)acrylat-Basis zur Verfügung zu stellen.The object was therefore to improve plastisols with Performance properties, especially improved mechanical ones Properties and sufficient storage stability To provide polyalkyl (meth) acrylate base.

Es wurde nun gefunden, daß die vorliegende Erfindung diese Aufgabe weitgehend löst, insbesondere da sie eine große Variationsbreite bei der Einstellung des Weichmachergehalts und damit der mechanischen Eigenschaften erlaubt, ohne daß ins Gewicht fallende Viskositätsprobleme auftreten. Es ist überraschend, daß trotz des hohen Anteils an reaktiven Monomeren die Lagerstabilität nicht beeinträchtigt wird. Für den Gegenstand der vorliegenden Erfindung wird aus unmittelbar verständlichem Grund der Ausdruck "Reaktivplastisole" vorgeschlagen.It has now been found that the present invention accomplishes this objective largely solves, especially since there is a large range of variation in the Adjustment of the plasticizer content and thus the mechanical Properties allowed without being significant Viscosity problems occur. It's surprising that despite the high Proportion of reactive monomers does not affect the storage stability will. For the subject matter of the present invention, from immediately understandable reason the expression "reactive plastisols" suggested.

Die Erfindung betrifft somit Reaktivplastisole enthaltend

  • (A) Thermisch verfilmbare Polymere P als Basispolymer für Plastisole, insbesondere Polystyrol und Polyvinylester, Copolymere oder Poly(meth)acrylsäureester, speziell disperse Poly(meth)acrylsäureester P-M, vorzugsweise in Form eines sprühgetrockneten Emulsionspolymerisats,
  • (B) einen reaktiven Monomeranteil bestehend aus mindestens einem monofunktionellen (Meth)acrylatmonomeren RM der Formel I
    Figure 00050001
       worin
    R
    Wasserstoff oder Methyl bedeuten und
       wobei gilt n=0, 1 bis 20 ;
          P= Alkylen -(CH2)m-O-
          m= 1-6, wobei die Alkylengruppe auch verzweigt sein kann,
          Q= Alkylreste, mit 1-14 Kohlenstoffatomen, wobei der Alkylrest auch verzweigt sein kann,
          ferner:
    • Cycloalkyl, polycyclischer Alkylrest
    • aromatischer Rest, Phenylrest
    • substituierte Aromaten
    • Aryloxyreste
    • Heterocyclus
    • Wasserstoff;
  • (C) mindestens einen, mit dem thermisch verfilmbaren Polymeren verträglichen niedermolekularen oder oligomeren Weichmacher W
  • (D) weiteren vernetzenden Monomeren VM
  • (E) an sich bekannte Füllstoffe, Pigmente und Hilfsstoffe.
    • The invention thus relates to containing reactive plastisols
  • (A) Thermally filmable polymers P as base polymer for plastisols, in particular polystyrene and polyvinyl esters, copolymers or poly (meth) acrylic esters, especially disperse poly (meth) acrylic esters PM, preferably in the form of a spray-dried emulsion polymer,
  • (B) a reactive monomer component consisting of at least one monofunctional (meth) acrylate monomer RM of the formula I.
    Figure 00050001
    wherein
    R.
    Mean hydrogen or methyl and
    where n = 0.1 to 20;
    P = alkylene - (CH 2 ) m -O-
    m = 1-6, where the alkylene group can also be branched,
    Q = alkyl radicals with 1-14 carbon atoms, whereby the alkyl radical can also be branched,
    further:
    • Cycloalkyl, polycyclic alkyl radical
    • aromatic radical, phenyl radical
    • substituted aromatics
    • Aryloxy residues
    • Heterocycle
    • Hydrogen;
  • (C) at least one low molecular weight or oligomeric plasticizer W which is compatible with the thermally filmable polymer
  • (D) further crosslinking monomers VM
  • (E) fillers, pigments and auxiliaries known per se.
    •

    Wie bereits vorstehend beschrieben, sind die thermisch verfilmbaren Polymeren P als Basispolymere für Plastisole an sich bekannt. As already described above, they are thermally filmable Polymers P are known per se as base polymers for plastisols.

    Von besonderer Bedeutung ist die vorliegende Erfindung im Hinblick auf die aus Poly(meth)acrylsäureestern P-M gebildeten, sogenannten PAMA-Plastisole. Der Polymeranteil liegt vorzugsweise in disperser Form, insbesondere als sprühgetrocknetes Emulsionspolymerisat vor.The present invention is of particular importance with regard to the so-called PAMA plastisols formed from poly (meth) acrylic acid esters P-M. The polymer content is preferably in disperse form, in particular as a spray-dried emulsion polymer.

    Komponente (A)Component (A)

    Der hauptsächliche Monomerbestandteil des thermisch verfilmbaren Polymeren P ist bevorzugt das Methylmethacrylat oder Styrol, die in der Regel über 60 Gew.-% insbesondere > 70 und vorzugsweise 80 - 99 Gew.-%, bezogen auf P-M ausmachen.
    Bevorzugt ist weiterhin ein Gehalt an polaren Comonomeren in Mengen von 0 - 20 Gew.-%, bezogen auf P-M. Unter polaren Comonomeren seien besonders solche verstanden, die die Heteroatome Stickstoff und/oder Sauerstoff oder - weniger bevorzugt Schwefel - enthalten, insbesondere wenn sie gleichzeitig daran gebundenen Wasserstoff aufweisen.    The main monomer component of the thermally filmable polymer P is preferably methyl methacrylate or styrene, which as a rule make up over 60% by weight, in particular> 70 and preferably 80-99% by weight, based on PM.
    A content of polar comonomers in amounts of 0-20% by weight, based on PM, is also preferred. Polar comonomers are to be understood as meaning, in particular, those which contain the heteroatoms nitrogen and / or oxygen or - less preferably sulfur - especially if they have hydrogen bonded to them at the same time.

    Vorzugsweise bestehen die polaren Comonomeren aus Verbindungen der Formel II

    Figure 00070001
    worin

    R'
    für Wasserstoff oder Methyl und
    R1
    für -OH oder -NHR2, wobei R2 Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen bedeutet, der auch verzweigt sein kann,
    oder einen Hydroxyester - O - R3 - OH, wobei R3 ein
    Alkylenrest mit 1 bis 6 Kohlenstoffatomen bedeutet, der auch verzweigt sein kann.
    oder werden ausgewählt aus der Gruppe: Maleinsäure, Maleinsäureanhydrid, Furmarsäure oder Itaconsäure.
    The polar comonomers preferably consist of compounds of the formula II
    Figure 00070001
    wherein
    R '
    for hydrogen or methyl and
    R1
    for -OH or -NHR 2 , where R 2 is hydrogen or an alkyl radical with 1 to 6 carbon atoms which can also be branched,
    or a hydroxy ester - O - R 3 - OH, where R 3 is a
    Means alkylene radical with 1 to 6 carbon atoms, which can also be branched.
    or are selected from the group: maleic acid, maleic anhydride, fumaric acid or itaconic acid.

    Genannt seien insbesondere die (Meth)acrylsäure und das (Meth)acrylamid.(Meth) acrylic acid and (meth) acrylamide may be mentioned in particular.

    Neben Methylmethacrylat und dem polaren Comonomeren können die Poly(meth)acrylsäureester P-M noch von MMA verschiedene Momomere der Formel III

    Figure 00080001
    worin

    R"
    für Wasserstoff oder Methyl und
    R2
    für einen Alkylrest mit 1 bis 10 Kohlenstoffatomen steht, der gegebenenfalls verzweigt sein kann, sowie für einen Cycloalkylrest mit 3 - 7 Ringgliedern steht.
    In addition to methyl methacrylate and the polar comonomer, the poly (meth) acrylic acid esters PM can also contain monomers of the formula III other than MMA
    Figure 00080001
    wherein
    R "
    for hydrogen or methyl and
    R2
    represents an alkyl radical with 1 to 10 carbon atoms, which may optionally be branched, and represents a cycloalkyl radical with 3-7 ring members.

    Vorzugsweise handelt es sich bei den Monomeren der Formel III um C4-Alkylester der Acrylsäure oder der Methacrylsäure, z.B. Isobutyl(meth)acrylat oder n-Butyl(meth)acrylat oder um Ethylhexylmethacrylat, Isobornylmethacrylat, Cyclohexylmethacrylat.The monomers of the formula III are preferably C4-alkyl esters acrylic acid or methacrylic acid, e.g. Isobutyl (meth) acrylate or n-butyl (meth) acrylate or around Ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate.

    Von besonderem Interesse sind Poly(meth)acrylsäureester P-M mit Kern-Schale-Aufbau.Poly (meth) acrylic acid esters P-M with a core-shell structure are of particular interest.

    Als Richtwert für den Gehalt der efindungsgemäßen Reaktivplastisole an den thermisch verfilmbaren Polymeren, insbesondere auf PMMA-Basis seien 60 bis 10 Gewichtsprozent, bezogen auf die Gesamtmasse der Komponenten (A) - (E), speziell ca. 40 Gew.-%, angegeben.As a guide value for the content of the reactive plastisols according to the invention the thermally filmable polymers, especially those based on PMMA be 60 to 10 percent by weight, based on the total mass of Components (A) - (E), specifically about 40% by weight, are given.

    Im allgemeinen liegt das Molekulargwicht Mw der Poly(meth)acrylsäurrester P-M im Bereich 20 000 bis 200 000, insbesondere 30 000 bis 150 000 Dalton.In general, the molecular weight Mw is the Poly (meth) acrylic acid ester P-M in the range 20,000 to 200,000, especially 30,000 to 150,000 daltons.

    Komponente (B)Component (B)

    Die die reaktive Monomerkomponente (B) bildenden monofunktionellen (Meth)acrylatmonomeren RM entsprechen der Formel I

    Figure 00090001
    worin

    R
    für Wasserstoff oder Methyl stehen und
    wobei gilt
    n =
    0,1 bis 20
    P =
    Alkylen -(CH2)m-O-
    m =
    1 - 6, wobei die Alkylengruppe auch erzweigt sein kann,
    Q =
    Alkylreste, mit 1 bis 14 Kohlenstoffatomen, wobei der Alkylrest auch verzweigt sein kann, ferner:
    • Cycloalkyl, polycyclischer Alkylrest
    • aromatischer Rest, Phenylrest
    • substituierte Aromaten
    • Aryloxyreste
    • Heterocyklus
    • Wasserstoff
    The monofunctional (meth) acrylate monomers RM which form the reactive monomer component (B) correspond to the formula I.
    Figure 00090001
    wherein
    R.
    stand for hydrogen or methyl and
    where applies
    n =
    0.1 to 20
    P =
    Alkylene - (CH 2 ) m -O-
    m =
    1 - 6, whereby the alkylene group can also be branched,
    Q =
    Alkyl radicals with 1 to 14 carbon atoms, where the alkyl radical can also be branched, furthermore:
    • Cycloalkyl, polycyclic alkyl radical
    • aromatic radical, phenyl radical
    • substituted aromatics
    • Aryloxy residues
    • Heterocycle
    • hydrogen

    Genannt seien insbesondere Isobornylmethacrylat, Ethylhexylmethacrylat, Dicyclopentadienyloxyethylmethacrylat, Benzylmethacrylat, Hydroxyethylmethacrylat, Hydroxypropylmethacrylat, 2-Cyclohexyliden-4-methacryloyloxy-methyl-1,3-dioxolan, 2,2-Dimethyl-4-methacryloyloxy-methyl-1,3-dioxolan; 2,2-Dimethyl-5-ethyl-5-methacryloxy-methyl-1,3-dioxan, 5-Methacryloyloxymethyl-5-methyl-1,3-dioxan, 2-Phenyl-1,3-dioxolan-4-yl-methylmethacrylat, Phenylethylmethacrylat, Phenoxyehtylmethacrylat, Ethyltriglycolmethacrylat, Furfurylmethacrylat, Tetrahydrofurfurylmethacrylat (Vgl. US 2.680.735; BE-A 521 281) Isobornyl methacrylate, ethylhexyl methacrylate, Dicyclopentadienyloxyethyl methacrylate, benzyl methacrylate, Hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-cyclohexylidene-4-methacryloyloxy-methyl-1,3-dioxolane, 2,2-dimethyl-4-methacryloyloxy-methyl-1,3-dioxolane; 2,2-dimethyl-5-ethyl-5-methacryloxy-methyl-1,3-dioxane, 5-methacryloyloxymethyl-5-methyl-1,3-dioxane, 2-phenyl-1,3-dioxolan-4-yl-methyl methacrylate, Phenylethyl methacrylate, phenoxyethyl methacrylate, Ethyl triglycol methacrylate, furfuryl methacrylate, Tetrahydrofurfuryl methacrylate (cf. US 2,680,735; BE-A 521 281)

    Dem Anteil der reaktiven Monomeren (B) entsprechend setzt man den Formulierungen zweckmäßigerweise Radikal-Initiatoren, wie die bereits für die Herstellung der Poly(meth)acrylsäureester P-M beschriebenen, in Mengen von etwa 0,5 Gew.-%, bezogen auf die reaktiven Monomeren (B) zu.The proportion of reactive monomers (B) is set according to the Formulations expediently radical initiators, such as those already for the preparation of the poly (meth) acrylic acid esters P-M described in Quantities of about 0.5% by weight, based on the reactive monomers (B) to.

    Desweiteren enthalten die erfindungsgemäßen Reaktivplastisole noch als weitere vernetzende Monomerkomponente (D) an sich bekannte Vernetzer in Mengen von bis 20 Gew.-% vorzugsweise 0,1 bis 10 Gew.-%, bezogen auf die thermisch verfilmbaren Polymeren P. Solche vernetzende Monomere enthalten mehrere radikalisch polymerisierbare Einheiten in gleichem Molekül, wie beispielsweise (Meth)acrylsäureester mehrwertiger Alkohole.
    Genannt seien z.B. Trimethylolpropan-tri(meth)acrylat, 1,4-Butandioldimethacrylat, 1,3-Butandioldimethacrylat, 1,6-Hexandioldimethacrylat.    The reactive plastisols according to the invention also contain, as further crosslinking monomer component (D), known crosslinkers in amounts of up to 20% by weight, preferably 0.1 to 10% by weight, based on the thermally filmable polymers P. Such crosslinking monomers contain several radically polymerizable units in the same molecule, such as, for example, (meth) acrylic acid esters of polyhydric alcohols.
    Examples include trimethylolpropane tri (meth) acrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate.

    Die Komponente (A) und (B) stehen in der Regel im Gewichtsverhältnis 20 zu 1 bis 1 zu 20.Components (A) and (B) are generally in a weight ratio of 20 to 1 to 1 to 20.

    Die Herstellung von dispersem Poly(meth)acrytsäureestern P-M durch Sprühtrocknung von Polymerdispersionen ist an sich bekannt (vgl. H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen loc. cit. S. 217 - 299; Kirk-Othmer, 3 rd Ed. Vol. 1, loc. cit. pg. 397 - 400; EP-B 0 294 663). Man arbeitet in an sich bekannter Weise, wobei neben den Monomeren als Medium (vorzugsweise destilliertes) Wasser, ein wasserlöslicher Initiator und ein Emulgator zur Anwendung kommen. The production of disperse poly (meth) acrylic acid esters PM by spray-drying polymer dispersions is known per se (cf. H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen loc. Cit. Pp. 217-299; Kirk-Othmer, 3 rd Ed. Vol. 1 , loc. cit. pg. 397-400; EP-B 0 294 663). The procedure is known per se, using not only the monomers but also water, a water-soluble initiator and an emulsifier as the medium (preferably distilled).

    Als Emulgatoren kommen ebenfalls die üblichen mit einem HLB-Wert über 12, insbesondere anionische Emulgatoren, wie z.B. die Salze langkettiger Paraffinsulfonsäure infrage.The usual emulsifiers also come with an HLB value over 12, especially anionic emulsifiers, such as the salts long-chain paraffin sulfonic acid is an option.

    Bei einer bevorzugten Ausführungsform verfährt man so, daß man zu einer wäßrigen Vorlage mit Initiator/Emulgator bei erhöhter Temperatur, beispielsweise ca. 80 °C, eine wäßrige Emulsion der Monomeren mit Initiator unter Rühren innerhalb einer gewissen Zeit, beispielsweise 1 ½ (± ½) Stunde zutropfen läßt und zur Vervollständigung der Polymerisation noch etwa über den gleichen Zeitraum bei erhöhter Temperatur hält. Nach dem Abkühlen kann der Reaktionsansatz sprühgetrocknet werden.In a preferred embodiment, the procedure is such that one to an aqueous template with initiator / emulsifier at elevated temperature, for example about 80 ° C, an aqueous emulsion of the monomers with Initiator with stirring within a certain time, for example 1½ (± ½) hour added dropwise and to complete the polymerization holds for about the same period at an elevated temperature. To After cooling, the reaction mixture can be spray-dried.

    Als Initiator haben sich anorganische Peroxide wie Kalium- oder Ammoniumperoxidisulfat in Mengen von 0,001 bis 0,2 Gew.-%, bezogen auf die Monomeren bewährt. Auch Redoxsysteme bestehend aus einer Peroxidkomponente und einer reduzierenden Komponente wie z.B. einem reduzierenden Salz einer Schwefel-Sauerstoffsäure lassen sich verwenden.Inorganic peroxides such as potassium or Ammonium peroxydisulfate in amounts of 0.001 to 0.2% by weight, based on proven on the monomers. Also redox systems consisting of a Peroxide component and a reducing component such as a reducing salt of an oxo-sulfuric acid can be use.

    Zur Herstellung der Polymerisate P-M kann das Molekulargewicht durch Zusatz von Reglern, gewöhnlich von Schwefelreglern, insbesondere von Alkylmercaptanen wie z.B. Dodecylmercaptan, Laurylmercaptan in Mengen von gewöhnlich ca. 0,05 bis 0,5 Gew.-%, bezogen auf die Monomeren geregelt werden. Das Molgewicht liegt im allgemeinen im Bereich 20 000 - 200 000 Dalton. To prepare the polymers P-M, the molecular weight can by Addition of regulators, usually sulfur regulators, especially Alkyl mercaptans such as dodecyl mercaptan, lauryl mercaptan in Amounts of usually about 0.05 to 0.5 wt .-%, based on the Monomers are regulated. The molecular weight is generally in Range 20,000-200,000 daltons.

    Auch die Sprühtrocknung kann in bekannter Weise erfolgen. Großtechnisch werden sogenannte Sprühtürme verwendet, die üblicherweise im Gleichstrom mit der eingesprühten Dispersion von oben nach unten mit Heißluft durchströmt werden. Die Dispersion wird durch eine oder viele Düsen versprüht oder bevorzugt mittels einer schnell rotierenden Lochscheibe zerstäubt. Die eintretende Heißluft hat eine Temperatur von 100 °C bis 250 °C, vorzugsweise von 150 °C - 250 °C.Spray drying can also be carried out in a known manner. So-called spray towers are used on a large scale usually in cocurrent with the dispersion sprayed in from above be flowed through with hot air downwards. The dispersion is through one or many nozzles sprayed or preferably by means of one quickly rotating perforated disc atomized. The incoming hot air has a Temperature from 100 ° C to 250 ° C, preferably from 150 ° C to 250 ° C.

    Für die Eigenschaften des sprühgetrockneten Emulsionspolymerisats ist die Austrittstemperatur der Luft entscheidend, d.h. die Temperatur, bei der die getrockneten Pulverkörnchen am Fuß des Sprühturms oder in einem Zyklonabscheider von dem Luftstrom getrennt werden. Diese Temperatur soll möglichst unter der Temperatur liegen, bei der das Emulsionspolymerisat sintern oder schmelzen würde. In vielen Fällen ist eine Austrittstemperatur von 50 °C - 90 °C gut geeignet.For the properties of the spray-dried emulsion polymer is the outlet temperature of the air is decisive, i.e. the temperature at which the dried powder granules at the base of the spray tower or in separated from the air flow by a cyclone separator. These The temperature should be below the temperature at which the Emulsion polymer would sinter or melt. In many cases it is an outlet temperature of 50 ° C - 90 ° C is well suited.

    Die Austrittstemperatur läßt sich bei konstantem Luftstrom durch Variation der kontinuierlich je Zeiteinheit eingesprühten Dispersionsmenge regeln.The outlet temperature can be varied with a constant air flow regulate the amount of dispersion continuously sprayed in per unit of time.

    Die durch Sprühtrocknung der Polymerdispersion gewonnen Polymerisate P-M weisen eine Primärteilchengröße im Bereich 0,1 bis 5 µm auf. (Bestimmung nach Ullmanns Encyclopädie der techn. Chemie 4. Auflage Bd. 5, S. 725 - 752). Die Korngrößenverteilung kann durch Messung der Lichtextinktion einer durch die Meßzelle eines Meßgeräts ("Kratel Partoskop F" er Kratel GmbH, Göttigen) strömenden Suspension der Teilchen in Wasser bestimmt werden. Eine sekundär erfolgende Aggregation der Primärteilchen kann zu Agglomeraten im Größenbereich 5 - 100 µm führen, die aber gleichfalls im Sinne der vorliegenden Erfindung verwendbar sind. The PM polymers obtained by spray drying the polymer dispersion have a primary particle size in the range from 0.1 to 5 μm. (Determination according to Ullmann's Encyclopedia of Technological Chemistry, 4th Edition, Vol. 5 , pp. 725-752). The particle size distribution can be determined by measuring the light absorbance of a suspension of the particles in water flowing through the measuring cell of a measuring device ("Kratel Partoskop F" from Kratel GmbH, Göttigen). A secondary aggregation of the primary particles can lead to agglomerates in the size range 5-100 μm, but these can also be used for the purposes of the present invention.

    Komponente (C)Component (C)

    Als Weichmacher W der Kategorie (C) kommen an sich bekannte Weichmacher infrage, wie z. B. die Alkylester der Phthalsäure, der Adipinsäure, der Sebacinsäure, chlorierte Paraffine, Trialkylphosphate, aliphatische oder araliphatische Polyester neben Weichmachern mit mittlerer Polarität wie höhere Polyglykole, Phthalsäurepolyester oder Adipinsäurepolyester u. v. a. Als ein Hinweis kann gelten, daß in der Regel auch alle für PVC geeigneten Weichmacher eingesetzt werden können, wobei die Gruppe der Phthalat-Weichmacher wegen ihrer herausragenden technischen Bedeutung besonders hervorzuheben ist. Eine ausführliche Beschreibung geeigneter Weichmacher findet sich im Kunststoff-Handbuch Herausg. H.K. Felger Bd. 1/1 C, Hanser Verlag 1985 sowie in H.F. Mark et al. Encyclopedia of Polymer Science and Engineering, Supplemental Volume pg. 568 - 647, J. Wiley 1989. Eine Auswahl geeigneter Weichmacher kann auch der DE-C 25 43 542 entnommen werden.Plasticizers W of category (C) are known per se Plasticizers in question, such as B. the alkyl esters of phthalic acid, the Adipic acid, sebacic acid, chlorinated paraffins, trialkyl phosphates, aliphatic or araliphatic polyester in addition to plasticizers with medium polarity such as higher polyglycols, phthalic acid polyester or Adipic acid polyester; a. A hint can be that in the As a rule, all plasticizers suitable for PVC can also be used can, taking the group of phthalate plasticizers because of their outstanding technical importance is particularly to be emphasized. A detailed description of suitable plasticizers can be found in Kunststoff-Handbuch ed. H.K. Felger Vol. 1/1 C, Hanser Verlag 1985 as well as in H.F. Mark et al. Encyclopedia of Polymer Science and Engineering, Supplemental Volume pg. 568-647, J. Wiley 1989. One DE-C 25 43 542 can also select suitable plasticizers can be removed.

    Besonders erwähnt seien das Benzyl-octylphthalat, weiter Diisodecylphthalat, Dioctylphthalat.
    Die Weichmacher W kommen in der Regel in Anteilen von 5 bis 200 Gew.-Teilen, auf 100 Gew.-Teile der thermisch verfilmbaren Polymeren P zur Anwendung. Das Verhältnis zwischen Weichmacher W und den Monomeren der Komponente (B) läßt sich praktisch beliebig einstellen.     Benzyl octyl phthalate, further diisodecyl phthalate and dioctyl phthalate may be mentioned in particular.
    The plasticizers W are generally used in proportions of 5 to 200 parts by weight per 100 parts by weight of the thermally filmable polymers P. The ratio between plasticizer W and the monomers of component (B) can be adjusted practically as desired.

    Bereits durch einen Anteil der Monomer-Komponente (B) von 10 Gew.-% erhält man im allgemeinen verbesserte Produkteigenschaften. Eine übliche Rezeptur enthält beispielsweise 10 Gew.-Teile Monomeranteile (B) [inclusive 0,5 Gew.-% Initiator bezogen auf den Gehalt (B)] ca. 40 Gew.-Teile thermisch verfilmbare Polymere P, 50 Gew.-Teile Weichmacher W.Even with a proportion of the monomer component (B) of 10% by weight generally improved product properties are obtained. One The usual formulation contains, for example, 10 parts by weight of monomer (B) [including 0.5% by weight of initiator based on content (B)] approx. 40 Parts by weight of thermally filmable polymers P, 50 parts by weight Plasticizer W.

    Die erhaltenen erfindungsgemäßen Plastisole weisen sehr gute Gebrauchseigenschaften auf. Hervorzuheben ist z.B. ihre Zugfestigkeit und die Blockfestigkeit der Produkte. Topfzeiten von mehr als 30 Tagen sind gewährleistet. Vergleichsprodukte mit einem Gehalt von 40 Gew.-% Polymer und 60 Gew.-% Weichmacher weisen eine sehr geringe Zugfestigkeit und eine klebrige Oberfläche auf.
    Das Verhältnis zwischen Weichmacher und Komponente (C) läßt sich beliebig einstellen.    The resulting plastisols according to the invention have very good performance properties. Their tensile strength and the blocking resistance of the products should be emphasized, for example. Pot lives of more than 30 days are guaranteed. Comparative products with a content of 40% by weight of polymer and 60% by weight of plasticizer have a very low tensile strength and a sticky surface.
    The ratio between plasticizer and component (C) can be adjusted as desired.

    Komponente (E)Component (E)

    Die Reaktivplastisole enthalten anwendungsbedingt noch an sich bekannte Hilfsstoffe wie Haftvermittler, Netzmittel, Verlaufsmittel, Treibmittel in Anteilen bis 5 Gew.-% (bezogen auf die Reaktivplastisole) enthalten. (Vgl. Ullmann's Encyclopedia of Industrial Chemistry 5 th Ed. Vol. A21, pg. 734 - 737 VCH 1992). Depending on the application, the reactive plastisols still contain auxiliaries known per se, such as adhesion promoters, wetting agents, leveling agents, propellants in proportions of up to 5% by weight (based on the reactive plastisols). (. See Ullmann's Encyclopedia of Industrial Chemistry 5th Ed Vol A21, pg 734 -... 737 VCH 1992).

    Herstellung von PlastisolenProduction of plastisols

    Prinzipiell kann die Mischung der Komponenten für die erfindungsgmäßen Reaktivplastisole mit verschiedenartigen Mischern vorgenommen werden. Im Einklang mit den Erfahrungen bei PVC- und PAMA-Plastisolen werden jedoch langsam laufende Planeten-Rührwerke, Hochgeschwindigkeits-Mischer bzw. Dissolver, Horizontal-Turbomischer und Dreiwalzenwerke bevorzugt; wobei die Wahl von der Viskosität der erzeugten Plastisole beeinflußt wird. (Vgl. H.F. Mark et al., Encyclopedia of Polymer Science and Engineering 2 nd Ed. Vol. 17, 365 - 866 J. Wiley 1989). Gemischt wird, bis Homogenisierung der Masse eingetreten ist.In principle, the components for the reactive plastisols according to the invention can be mixed using various types of mixers. In accordance with the experience with PVC and PAMA plastisols, however, slow-running planetary agitators, high-speed mixers or dissolvers, horizontal turbo mixers and three-roll mills are preferred; the choice being influenced by the viscosity of the plastisols produced. (. See HF Mark et al, Encyclopedia of Polymer Science and Engineering 2nd Ed Vol 17, 365 -... 866 J. Wiley 1989). Mixing is carried out until the mass has become homogeneous.

    Die Masse kann in Schichtstärken von 1 - 5 mm in Falle von PAMA-Plastisolen vorzugsweise bei Temperaturen von 100 - 200 °C, im allgemeinen innerhalb von 30 bis 2 Minuten geliert werden. Man erhält in der Regel eine transparente flexible Folie.In the case of PAMA plastisols, the mass can be layered in thicknesses of 1 - 5 mm preferably at temperatures of 100-200 ° C, im generally be gelled within 30 to 2 minutes. You get in usually a transparent flexible film.

    Anwendung der PlastisoleApplication of plastisols

    Die gemäß der vorliegenden Erfindung erhältliche Reaktivplastisole sind für vielerlei Anwendungen geeignet, wie sie beispielsweise durch die Anwendungsbereiche für PVC- und PAMA-Plastisole vorgezeichnet sind: Textilbeschichtungsmittel, Fußbodenbelag z.B. flexible Bodenbeläge, Unterbodenschutz, Punktschweißpasten oder Beschichtungsmittel für flexible Substanzen. The reactive plastisols obtainable according to the present invention are suitable for many applications, for example by the Areas of application for PVC and PAMA plastisols are: Textile coating agents, floor coverings e.g. flexible floor coverings, Underbody protection, spot welding pastes or coating agents for flexible substances.

    Vorteilhafte WirkungenBeneficial effects

    Durch den Einbau von polaren Comonomeren gemäß der Formel (II) in die Polymeren nach (A) z.B. auch im Zuge einer Kern-Schale-Polymerisation, wird das Anquellen der Polymeren durch die reaktiven Monomeren der Gruppe (B) unterbunden.The incorporation of polar comonomers according to the formula (II) in the polymers according to (A) e.g. also in the course of a core-shell polymerization, the swelling of the polymers is caused by the reactive Group (B) monomers prevented.

    Die Komponente (B) weist insbesondere folgende Vorzüge auf:Component (B) has the following advantages in particular:

    In Abwesenheit von Weichmacher weisen die Monomere nach (B) in polymerisiertem Zustand in der Regel eine gute Verträglichkeit mit den Polymeren nach (A) auf.In the absence of plasticizer, the monomers according to (B) in polymerized state generally good compatibility with the Polymers according to (A).

    Die Monomeren nach (B) haben einen sehr hohen Siedepunkt und weisen praktisch keinen nennenswerten Geruch auf.The monomers according to (B) have a very high boiling point and have practically no smell worth mentioning.

    Claims (10)

    1. Reactive plastisols containing
      (A) polymers which can be thermally processed into a film P known per se, as basic polymers for plastisols
      (B) a reactive monomer component consisting of at least one monofunctional (meth)acrylate monomer RM of the formula I
      Figure 00210001
         where R represents hydrogen or methyl and
         wherein n=0, 1 to 20;
         P= alkylene -(CH2)m-O-
            m= 1-6, while the alkylene group may also be branched,
         Q= alkyl groups having 1- 14 carbon atoms, while the alkyl group may also be branched, and
         also:
      cycloalkyl, polycyclic alkyl groups
      aromatic groups, phenyl groups
      substituted aromatics
      aryloxy groups
      heterocycle
      hydrogen;
      (C) at least one low-molecular or oligomeric plasticiser W which is compatible with the polymer P which can be thermally processed into a film
      (D) other cross-linking monomers VM
      (E) fillers, pigments and adjuvants which are known per se.
    2. Reactive plastisols according to claim 1, characterized in that the polymers P which can be thermally processed into a film consist of poly(meth)acrylates P-M based on polymethyl methacrylate.
    3. Reactive plastisols according to claim 2, characterized in that the poly(meth)acrylates have been used in the form of spray-dried emulsion polymers.
    4. Reactive plastisols according to claim 1, characterized in that the polymers P which can be thermally processed into a film consist of polystyrene or polystyrene copolymers.
    5. Reactive plastisols according to claim 4, characterized in that polystyrene or polystyrene copolymers are used in the form of spray-dried emulsion polymers.
    6. Reactive plastisols according to claims 2 to 5, characterized in that the poly(meth)acrylates P-M or the styrene copolymers have a content of 0-20 wt.-%, based on P-M, of polar comonomers.
    7. Reactive plastisols according to claim 6, characterised in that the polar comonomers are selected from the group consisting of (meth)acrylic acid or (meth)acrylamide, maleic acid, maleic anhydride, fumaric acid, itaconic acid.
    8. Reactive plastisols according to claims 1 to 7, characterized in that components (A) and (B) are in a weight ratio of from 1 : 20 to 20 : 1.
    9. Reactive plastisols according to claims 1 to 8, characterized in that the cross-linking monomers VM are used in amounts of from 0.1 to 15 wt.-%.
    10. Use of reactive plastisols according to one of the preceding claims as an underbody protection, as floor covering, as textile coating agent, as spot welding paste or as coating agent for flexible substances.
    EP98951411A 1997-09-20 1998-09-16 Materials which can be thermally coated with a polymerizable component Expired - Lifetime EP1017747B1 (en)

    Priority Applications (1)

    Application Number Priority Date Filing Date Title
    EP04005082A EP1426419A3 (en) 1997-09-20 1998-09-16 Thermically film forming compositions with a polymerisable component (Reactiv plastisols)

    Applications Claiming Priority (5)

    Application Number Priority Date Filing Date Title
    DE19741614 1997-09-20
    DE19741614 1997-09-20
    DE19827384 1998-06-19
    DE19827384A DE19827384A1 (en) 1997-09-20 1998-06-19 Thermally filmable compositions with a polymerizable component (reactive plastisols)
    PCT/EP1998/005880 WO1999015592A1 (en) 1997-09-20 1998-09-16 Materials which can be thermally coated with a polymerizable component

    Related Child Applications (1)

    Application Number Title Priority Date Filing Date
    EP04005082A Division EP1426419A3 (en) 1997-09-20 1998-09-16 Thermically film forming compositions with a polymerisable component (Reactiv plastisols)

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    EP1017747A1 EP1017747A1 (en) 2000-07-12
    EP1017747B1 true EP1017747B1 (en) 2004-11-10

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    EP (1) EP1017747B1 (en)
    JP (1) JP2001517721A (en)
    AT (1) ATE282069T1 (en)
    AU (1) AU9744398A (en)
    BR (1) BR9812656A (en)
    CA (1) CA2304054C (en)
    ES (1) ES2229542T3 (en)
    WO (1) WO1999015592A1 (en)

    Families Citing this family (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE10152441B4 (en) * 2001-10-26 2007-01-04 Dynea Moers Gmbh Use of an aqueous dispersion adhesive as a laminating adhesive
    DE102007032836A1 (en) 2007-07-12 2009-01-15 Evonik Röhm Gmbh Emulsion polymer containing activators, processes for its preparation and its use in two- or multi-component systems
    DE102008001583A1 (en) 2008-05-06 2009-11-12 Evonik Röhm Gmbh Emulsion polymer, is obtained by polymerizing mixture, where mixture comprises one or multiple monomers from mono-functional methacrylate monomers, styrene or vinyl, and copolymerizable monomer
    DE102008001582A1 (en) 2008-05-06 2009-11-12 Evonik Röhm Gmbh Two or multi component system, useful e.g. in adhesives, comprises an emulsion polymer, ethylenically unsaturated monomers, peroxides, unsaturated oligomers, polymerization inhibitors; and auxiliary and additive materials
    FR2981652B1 (en) 2011-10-21 2015-03-27 Arkema France COMPOSITIONS VIA IN-SITU POLYMERIZATION OF METHACRYLIC THERMOPLASTIC RESINS
    CN108192397B (en) * 2017-12-29 2020-09-22 北京东方雨虹防水技术股份有限公司 Modified acrylate spray film waterproof material and preparation method thereof

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    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4223115A (en) * 1978-04-24 1980-09-16 Lord Corporation Structural adhesive formulations
    JPS63185630A (en) * 1987-01-29 1988-08-01 東洋鋼板株式会社 Manufacture of steel plate coated with high-hardness vinyl chloride
    US4900771A (en) * 1989-01-26 1990-02-13 Aster, Inc. Hot applied plastisol compositions

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    ATE282069T1 (en) 2004-11-15
    AU9744398A (en) 1999-04-12
    ES2229542T3 (en) 2005-04-16
    WO1999015592A1 (en) 1999-04-01
    BR9812656A (en) 2000-08-22
    JP2001517721A (en) 2001-10-09
    CA2304054C (en) 2008-03-11
    US6288190B1 (en) 2001-09-11
    CA2304054A1 (en) 1999-04-01
    EP1017747A1 (en) 2000-07-12

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